Ds. Black et al., OBSERVATIONS ON THE MECHANISM OF HALOGEN-BRIDGE CLEAVAGE BY UNIDENTATE LIGANDS IN SQUARE-PLANAR PALLADIUM AND PLATINUM COMPLEXES, Australian Journal of Chemistry, 47(2), 1994, pp. 217-227
Cyclo-palladation and -platination of nitrogen donor ligands lead to i
nsoluble mu-chloro dimers which give mu-bromo and mu-iodo dimers on me
tathesis with the appropriate lithium halide. Addition of pyridine or
2,6-dimethylpyridine to the cyclopalladated dimers gives monomeric com
plexes with the halogen trans to the metal-carbon bond, whereas additi
on of 2,6-dimethylpyridine to the cycloplatinated complexes gives the
isomer with the halogen cis to the metal-carbon bond. The results are
discussed in terms of the mechanism of the bridge cleavage reaction.